Treatment of hydrocarbon oil



Dc. 21, 1937. c. P. DUBBS I TREATMENT OF HYDROCARBON OILS UIN Original Filed July 19. 1930 um; MV;

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Patented Dec. 21, 1937 l UNITED STATES PATENT OFFICE TREATMENT OF HYDROCARBON OIL Carbon P. Dubbs, Chicago, Ill., assignor, by mesne assignments, to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware j 4 Application July 19, 1930, Serial No. 469,201

v Renewed November 6, 1935 I s claims. (ci. nui-4t)y This invention relatestc thev treatment: of hythrough line'24 controlled by valve 25. A portion drocarbon oils,l and. refers more particularly to of the'productmay be recirculated through line the conversion vofVv higher boilinghydnocarbons 2Bby` means of lpump 21 controlling the same* f into lower lboiling'hydrocarbons suitable-'for moin additionl by valve 28;l 'fr 6 tot i'uel. `In one ofthe preferred embodiments; The' reiiux condensateleavng Idephlegmator 5 of my invention, theoil to be treatedissubjected I5, together with such charging oil as may have l inaheating zone to-conditions which will inducef beeni'ntroduced thereto,vr passes through line 23' cracking/thel oil thenbeingwithdrawnand suitcontrolled by valve y3l! andisfpicked' up by hotl i ablyreactedto separate vapors Afrom unvaporlzed oil'puinp 3|' and' sent t'oftheheatingv element 5` i* 10 residue. The unvaporized resdueis then flash throughflinef Z'Qfor reconversion. The unva- -10 distilled, the f vapors -resulting atherefromgbeing," porlzed residue'is' withdrawnffrom secondary 're` l further leonvertedltoproduce additional low Vboilationfchamber-'I2I through line 32l'co`ntrolled byl A. ing hydrocarbons t p. l vlv'e; and discharged into chamber-M A Y Furtherieaturesand objects ofinvention will Pressure ju'ponl chamber 34 issubs'ta'.r1'tially,re-2

becomeevident ,in the .followingldetailed deduced with respect to l"secondary reaction chamber 15 scriptionfof anapparatus and .process embodied I2, causing la Vsubstantial proportion vof the' oilvto withinthe concept Aof myy invention. A f, I i y. vaporize or iiash distill. rVaporized hydrocarbons Referringitovtheaccompanying drawing which are passed throughline 35 controlled by valve 35 l is ,a ,diagrammatic.. side elevationv view, `not to into secondary heating element' 31.v The temscale,l andA rwhich illustrates one form ,of my inperatures within this secondary heating element 20 vention: f. .i A 4 v are maintained suiiicientlyhigh to cause a sub-- Raw` oil chargingstock is pumped through stantial conversion ofI the-hydrocarbon 'vapors pump I, line 2 controlled byvalves 3 and 4, entering therein into lower boiling products, and and the heating element 5 located in furnace the operation is particularly directed towards i g5 setting 5. A .portion or all oitheraw charging high temperature or vapor phase conversion. 2g

oil may be introduced into fractionating zone I5 Where the productionV of gas is one of the prii through line 2' controlled by valve 3'. mary objects `of the process very high tempera- The oil at the conversion temperature is dis-` tures may bemaintained in this heating elecharged through line 1` controlled by valve 8 into ment.V For example, for the production of antiao primary reaction chamber 9. The unvaporized knock gasoline, ltemperatures from 950 degrees to 30 residual liquid, together with vapors, is contin- 1100 degrees F., more orless, may be maintained uously discharged into secondary reaction chamwithin this heating 'elementi For maximum gas ber I2 through line III controlled by valve Il. production temperatures from 1100 degrees to The continuous withdrawal of liquid trom the 1500 degrees F. are maintained.

primary reaction zone 3, maintaining practically The oil leaving heating element 31 is dis- 35 no liquid therein, permits a prolonged treatment charged through line 33 controlled by valve 39 of the hydrocarbons in substantially the vapor into fractionating zone I5, separating the lighter phase and prevents short-circuiting or bypassing from the heavier components ofthe vapors thereof the vapors, causing them to traverse the entire in,` During `some high temperature 'operations 40 length of the primary reaction zone. tarry material maybe formed and under these 40 The vapors containing the lower boiling prodconditions it is preferable to bypass the vapors ucts of conversion pass through line I3, confrom theheating element 31 throughadrip-pot or trolled by valve Il to the fractionating element trap 40. This is'accomplished by passing the I5. 'I'his element may be of any conventional vapors .through line 4I into drip-pot 40 and type and serves to separate by dephlegmation or' through line 42 back into line 38. Control valves 45 partial condensation the heavier intermediate 4I', A2', and 33 are manipulated accordingly. reflux condensate from the lower boiling prod- The unvaporized residue from flashing zone 3l ucts of the process. lThe vapors leaving fracis withdrawn through line I3 controlled by valve tionating zone I5 pass through line I6 con- IL Depending upon the tuansfer of temperature trolled by va1ve Il into `condenser I 8 and the and the reduction in pressure, that is, the tem-j 50 distillate is subsequently collected in receiver perature of the oil leaving the heating element 5, 2| alter `passing through line I9 controlled by this residue may have characteristicsl which make valve 20. The liquid collected in receiver 2l is Y it suitable for fuel oil or it may be reduced to o discharged to storage through line 22 controlled.; asphalt or even tocoke. Y by valve 23. The uncondensable gas'is passed Equalized pressures maybe used inthe primary 55 wise reduced pressure may be maintained upon the heating element 31 and the fractionating element I5. When it is desirable to carry the pressures upon heating element 31 and fractionating l element I above that maintained in the flashing zone, pump controlled by valves 31', 36' and 35 may be used.v

As specic examples of operating conditions and yields of production obtained by my process,

with a Mid-Continent topped crude oil 26 A. P I.`

gravity using a transfer temperature at the outlet of coil 5 of 930 degrees F., the temperatures within the primary and secondary reaction chambers being approximately 850 degrees and 810 degrees, respectively, and the pressures within these elements being approximately 170 pounds per square inch, with the reux ratio, that is, the proportion of reflux condensate returning to the heating element 5 through line 30 relative to the raw oil charging stock being fed to the system of 2.5:1, a yield was produced of approximately`55 percent of gasoline having an antiknock value or approximately percent benzol equivalent, that is, equivalent to a. mixture of Pennsylvania straight run gasoline containing 45 percent benzol. The transfer temperature at the outlet of heating element 31 during this operation was approximately 950 degrees F. A. yield of 30 percent unvaporized residual oil of ap- .proximately 12 Baume lgravity was produced.

This oil was suitable for` fuel oil containing less than 2 percent so-called B. S. or suspended carbonaceous matter. About 12 percent by weight of the oil was converted into gas by this operation, amounting to approximately 500 cubic feet of gas per barrel of oil charged. The remainder of the production constituted several percent of pressure distillate bottoms and a very small percentage of coke.

In another operation utilizing the same charging stock, by increasing the temperature in heating element 31 to approximately 1050 degrees F., approximately per cent of gasoline was made; approximately 25 per cent of fuel oil was produced of higher viscosity and somewhat lower gravity than .in the previous operation due to change brought about by the modified fractionation in column I5. The gas yield in this operation was approximately 1000 cubic feet per barrel, amounting to approximately 24 per cent by weight of the oil charged, a small percentage of pressure distillate bottomsand a somewhat larger percentage of coke than in the former operation was produced. The anti-knock value of the gasoline in this second operation was increased.

Using a gas, oil charging stock of approximately 36 A. P. I. gravity with corresponding conditions to the above produced higher yields of gasoline and fuel oil, the latter being of better quality than in the former operation, the gas produced being somewhat lower in quantity than the above.

Increasing temperatures in heating element 31 causes a greater conversion of the hydrocarbons into gas. This is also true of increased temperatures in heating element 5. For example, by maintaining temperatures at approximately 950 Temperatures of from 800 dedegrees F. in heating element 5 and 1050 degrees F. in heating element 31, I may make as much as 1500 to 2000 cubic feet of gas per barrel of oil charged, thus permitting the process to be utilized as a gas making operation in conjunction with .gasoline production.

When the formation of gas is undesirable it may to a large extent be reduced by employing relatively high pressure particularly in coil 31, say from 400 to 600 pounds per square inch.

The process above specifically described is capable of various modications, and the apparatus described for use in the process can be changed in various ways without departing from the concept of my invention. For example, although I have described the use of a preliminary andsecondary reaction chamber, a single reaction chamber may be used. This and other likely changes are included within the scope of the invention as outlined in the appended claims.

What I claim as my invention is:

1. A hydrocarbon oil cracking process which comprises passing the oil in a restricted stream through a. heating zone and heating the same therein to a cracking temperature under sufilcient pressure to maintain a substantial portion thereof in the liquid phase, discharging the heated oil into the upper portion of an enlarged reaction zone maintained under cracking conditions of temperature and pressure and passing the commingled vapors and liquid oil downwardly therethrough, withdrawing the vapors and liquid unvaporized oil as a mixture from the lower portion of the reaction zone and maintaining practically no liquid level in the reaction zone, separating the mixture withdrawn from the reaction zone into vapors and unvaporized oil and flash distilling the unvaporized oil by pressure reduction, subjecting vapors formed by the ilushing of the unvaporized oil to a gasoline-producing vapor phase cracking operation at vapor phase cracking temperature, dephlegmating the vapor phase cracked vapors in admixture with the vapors removed from the reaction zone to condense insuiciently cracked fractions of the commingled Vvapors and returning resultant reflux condensate to the heating zone, and nally condensing th dephlegmated vapors. 2. A hydrocarbon oil cracking process which comprises passing the oil in a restricted stream through a heating zone and heating. the same therein to a cracking temperature under suilcient pressure to maintain a substantial portion thereof in the liquid phase, discharging the heated oil into the upper portion of an enlarged reaction zone maintained under cracking conditions of temperature and pressure and passing the commingled vapors and liquid oil downwardly therethrough-withdrawing the vapors and liquid oil as a mixture from the lower portion of the reaction Zone and maintaining practically no liquid level in the reaction zone, introducing said mixture into a separating zone and separating the same therein into vapors and unvaporized oil, separately removing the vapors and unvaporized oil from the separating zone and ash distilling the latter by pressure reduction, subjecting thel resultant flashed vapors to a gasoline-producing vapor phase cracking operation and combining the cracked vapors thus formed with the vapors removed from the separating zone, deplegmating the resultant vaporous mixture to condense insuiiciently cracked fractions thereof and returning resultant reflux condensate to the heating zone, and iinally condensing the deplegmated vapors.

3. A conversion process which comprises passing hydrocarbon oil in a restricted stream through a heating zone and heating the sametherein to lcracking temperature under sufilcient pressure to maintain a substantial portion thereof in liquid phase, discharging the heated oil into the upper portion oi' an enlarged vertical reaction zone maintained under cracking conditions of temperature and pressure and passing resultant vapors and unvaporized oil downwardly therethrough, withdrawing the vapors and unvaporized oil from the lower portion of the reaction CARBON P. DUBBS.-

' CERTIFICATE OF CORRECTION.

Patent No. 2,102,889.

December 2l, 195'? CARBON P. DUBBS.

`Ii: is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows :Page 2, second column, Aline 52, claim l, strike out the word "liquid"; line 59, same claim, for "flushing" read flashing; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this lst day of March, A. D. 1958.

(Seal) Henry Van Arsdale,

Acting Conmiissioner' of Patents.

zone, and iinally condensing the deplegmated vapors.

3. A conversion process which comprises passing hydrocarbon oil in a restricted stream through a heating zone and heating the sametherein to lcracking temperature under sufilcient pressure to maintain a substantial portion thereof in liquid phase, discharging the heated oil into the upper portion oi' an enlarged vertical reaction zone maintained under cracking conditions of temperature and pressure and passing resultant vapors and unvaporized oil downwardly therethrough, withdrawing the vapors and unvaporized oil from the lower portion of the reaction CARBON P. DUBBS.-

' CERTIFICATE OF CORRECTION.

Patent No. 2,102,889.

December 2l, 195'? CARBON P. DUBBS.

`Ii: is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows :Page 2, second column, Aline 52, claim l, strike out the word "liquid"; line 59, same claim, for "flushing" read flashing; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this lst day of March, A. D. 1958.

(Seal) Henry Van Arsdale,

Acting Conmiissioner' of Patents. 

